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CN1041167A - Breathable microporous film and methods for making it - Google Patents

Breathable microporous film and methods for making it Download PDF

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Publication number
CN1041167A
CN1041167A CN89107315A CN89107315A CN1041167A CN 1041167 A CN1041167 A CN 1041167A CN 89107315 A CN89107315 A CN 89107315A CN 89107315 A CN89107315 A CN 89107315A CN 1041167 A CN1041167 A CN 1041167A
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China
Prior art keywords
microporous membrane
weight
further characterized
membrane according
film
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Pending
Application number
CN89107315A
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Chinese (zh)
Inventor
米歇尔·凯利·安通
戴维·詹姆斯·希尔
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Hercules LLC
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Hercules LLC
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Publication of CN1041167A publication Critical patent/CN1041167A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/15577—Apparatus or processes for manufacturing
    • A61F13/15707—Mechanical treatment, e.g. notching, twisting, compressing, shaping
    • A61F13/15731—Treating webs, e.g. for giving them a fibrelike appearance, e.g. by embossing
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/51—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the outer layers of the pads
    • A61F13/514—Backsheet, i.e. the impermeable cover or layer furthest from the skin
    • A61F13/51456—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties
    • A61F13/51458—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties being air-pervious or breathable
    • A61F13/5146—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties being air-pervious or breathable having apertures of perforations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/51—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the outer layers of the pads
    • A61F13/514—Backsheet, i.e. the impermeable cover or layer furthest from the skin
    • A61F13/51456—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties
    • A61F13/51458—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties being air-pervious or breathable
    • A61F13/51462—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties being air-pervious or breathable being defined by a value or parameter
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/18—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C08K7/20—Glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47G—HOUSEHOLD OR TABLE EQUIPMENT
    • A47G9/00—Bed-covers; Counterpanes; Travelling rugs; Sleeping rugs; Sleeping bags; Pillows
    • A47G2009/001—Anti-allergen; Anti-mite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/51—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the outer layers of the pads
    • A61F13/514—Backsheet, i.e. the impermeable cover or layer furthest from the skin
    • A61F13/51401—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by the material
    • A61F2013/51409—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by the material being a film
    • A61F2013/51411—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by the material being a film being impervious to fluids but not for air or vapours
    • A61F2013/51415—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by the material being a film being impervious to fluids but not for air or vapours with pores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/06—Molding microballoons and binder

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Epidemiology (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Public Health (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Biomedical Technology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Vascular Medicine (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Hematology (AREA)
  • Dermatology (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The present invention relates to a kind of method for preparing flexible microporous membrane, it is that 10～15 microns mineral filler or granulated glass sphere and dissolve as the mixture of the calcium stearate of processing aid mixes that this method comprises the polymkeric substance of alpha-olefin or multipolymer and 60～75% (weight) particle diameter, before making film, the water content of mixture keeps below 700/1000000ths, carry out biaxial stretching for 20～160 ℃ in temperature, each direction stretches 1.5～7 times.The Gurley porosity of the film that makes is 0.1～20 second; It can be used for the product that arbitrarily uses, slacks lining for example, and towel, sheet and hospital work clothes are if it can be used as accumulator diaphragm when filler is granulated glass sphere.

Description

Breathable microporous film and methods for making it
The present invention relates to the preparation method of flexible microporous membrane, the film that makes with described method and the application of these films.This film tensile strength height has good penetration or " ventilation property " to air and water vapour, and the infiltration of liquid towards water has high resistance to hydrostatic pressure.
As everyone knows, thermoplastic polymer can be filled with inert filler, casts sheet, and stretching forms the micropore thermoplastic film that aligns with desired gas or vapour permeability.For example, at United States Patent (USP) 3,903,234 and 4,698,372, british patent specification 2,151,538 and european patent application disclose 272, narrated the preparation method of these films in 026, last piece patent disclosure contain the film that homopolymer, multipolymer or its mixture of the α-monoolefine of 2 to 10 carbon atoms make, these films have the perviousness of oxygen and carbon dioxide about 77,500 and 155,000,000 milliliter/meter 2Between the one day-normal atmosphere.
United States Patent (USP) 4,698,372 has disclosed the microporous polymer film as the fabric quid pro quo, and it has the good moisture vapor transfer speed and the hydrostaticpressure of resistant to water penetration; About 25～35%(volume is formed and contained to these films by some ethylene copolymer) mineral filler, lime carbonate for example; They use a kind of processing aid (for example stearic acid), and this processing aid is considered to a kind of " inhibitor ", it is said that it can make the effective surface tension force of filler be reduced to value near matrix polymer.United States Patent (USP) 3,903,234 have disclosed the film of the biax orientation of gas-permeable, it is by containing 26～50%(weight) C of inorganic filler particle 2～C 10α-monoolefine polymer makes.British patent specification 2,151,538 discloses a kind of method for preparing the orientation film of water-water vapour penetration, and it is by containing 33～83%(weight) polyolefine of barium sulfate filler makes, as the leakage prevention sheet of disposable towel and health napkin.
In general, existing have sizable " ventilation property " do not reach required ventilation property every fluid film (for example drop cloth of those commercially available towel liners or slacks lining).This available Gurley number of pores evaluation quality, Gurley number of pores with ASTM D-726 method A or method B to measure second.(in theory, the Gurley number that records with method A is bigger 25 times than the Gurley number that records with method B, using method B in following specification sheets and claim).The method B of ASTM D-726 measure 10 milliliters of air under 12.2 English inch hydraulic pressure by one square of time (showing) that English inch microporous membrane is required with stopwatch, (ASTM D-726 method A measures 100 milliliters of air and passes through 1 square of required time of English inch microporous membrane under 4.9 English inch hydraulic pressure, shows with stopwatch).Be lower than the Gurley numerical table show microporous membrane to air (or wet air) pass through to produce hardly resistance, so Gurley number (being also referred to as the Gurley number of pores) is effectively measuring of ventilation property.
The Gurley number of general existing film is up to 100 seconds, usually more than 10 to 20 seconds.Having demonstrated needs reasonable price and has high-tensile and scratch flexible and unavailable micropore every fluid film than the softness of highly air-permeable, particularly hygienic articles industry more needs this film, for example make operational product with it, slacks lining for example, towel, the comfortable hospital work clothes that sheet and dress are nice and cool.Also need permeable films therefrom with ion-exchange capacity as accumulator diaphragm.
According to the present invention, a kind of method for preparing flexible microporous membrane, this film has high-tensile, air and water vapor had good penetration and " ventilation property ", the infiltration of liquid towards water has high resistance to hydrostatic pressure, method of the present invention comprises the steps: alpha-olefinic polymer or multipolymer, granulated filler and as the mixture melting mixing of the calcium stearate of processing aid, make film, and this film of biaxial stretching, it is characterized in that this mixture contains 60～75%(weight) particle diameter (referring to its diameter) be 10 to 15 microns mineral filler or granulated glass sphere, before making film, the water content of this blended composition remains on below the 700PPm, is about 20 to 160 ℃ of scopes from both direction to this film that stretches in temperature then, and each direction stretches and is approximately 1.5 to 7 times.
If the water content of said composition does not remain on below the 700ppm before making film, this is thin to use amount of filler of the presently claimed invention just can not stretch equably.The water content of blended composition preferably maintains below the 300PPm.
According to the present invention, have high-tensile, air and water vapor are had excellent permeability or " ventilation property ", the infiltration of liquid towards water has high hydrostatic pressure resistance and scratches the flexible microporous membrane according to the softness of the method for the invention manufacturing, its feature is that also it comprises:
20～37%(weight) contain the alpha-olefinic polymer or the multipolymer of 1-8 carbon atom,
60～75%(weight) particle diameter (referring to its diameter) is 10～15 microns mineral filler or a granulated glass sphere,
0.1～3%(weight) calcium stearate, Gurley porosity are 0.1 second to 20 seconds (measuring according to ASTM D-726 method B).
Preferred film of the present invention contains 0～2%(weight) stablizer.
" micropore " just is meant that this film comprises and manyly can leads to another surperficial open pore or passage from a surface, and the size in its hole can make air and water vapour by film, and the infiltration of liquid towards water has good resistance.In the Gurley number of pores, their porosity or ventilation property can be represented with rate of permeation, promptly use constant 44,64 * 10 9Just obtain rate of permeation (with milliliter/rice divided by Gurley number (method B) second 2One day-normal atmosphere is represented).The rate of permeation of microporous membrane of the present invention is greater than 44,64 * 10 9Second-milliliter/rice 2-sky-normal atmosphere is divided by 20 seconds, promptly greater than 2,232 * 10 9Or 2.232,000,000 milliliter/meter 2One day-normal atmosphere.
The size in the hole of packing material size decision microporous membrane of the present invention.Can expect that the hole that the less filler filler bigger than particle diameter of particle diameter produces is little.Spendable packing material size is not subjected to theoretic restriction among enforcement the present invention, but considers to adopt effective restriction from reality.Preferred footpath (referring to its diameter) should be 10～25 microns, and preferred filler is a lime carbonate, and its particle diameter (referring to its diameter) is about 12.5 microns.
Amount of filler has determined foundry goods (Casting) degree of the total porosity that drawn reaches to a great extent.Be lower than the lower limit of amount of filler scope, i.e. 60%(weight) time, according to the present invention when each direction stretches with maximal draw ratio (about 7 times), the reduced number in hole, the mutual binding between the hole is few, and film can not reach enough ventilation properties.The upper limit that is higher than the amount of filler scope, i.e. 75%(weight) time, these raw materials can not uniform mixing, and the foundry goods that is made by said composition can not stretch than (promptly 1.5 times) with minimum stretch of the present invention.Though can use other mineral filler,, can use granulated glass sphere to make filler if this film is used as accumulator diaphragm.
Calcium stearate processing aid coating filler particles impels the filler particles homodisperse, and can make said composition be stretched to required orientation degree.
The various alpha-olefinic polymer that contain 1～8 carbon atom can both be used as matrix polymer.Any alpha-olefin that presents enough tensile deformation and some tension set all can use.Come the selective polymerization raw material according to the required character of microporous membrane such as thermostability and nerve.Preferred polymkeric substance is polypropylene (PP), polyethylene (PE) (especially linear low density polyethylene (LLDPE)) and polybutene (PB), can certainly use ethene and propylene or with the multipolymer of the alpha-olefin of 4-8 carbon atom.For ease of processing, it is better than making body material with polypropylene separately to make body material with the mixture of linear low density polyethylene and polypropylene (ratio 95: 5) or polypropylene and the mixture of ethylene-propylene copolymer.
The selection of matrix polymer raw material and filler selection influence the optimal addn of filler and calcium stearate, the degree of orientation temperature and biax orientation.
With polypropylene/calcium carbonate composition, said composition preferably contains about 30%(weight) polypropylene and about 65%(weight) pearl filler.It is about 0.5～2.0% that the calcium stearate consumption is preferably, and is more preferably 2%, and the double orientation of film preferably stretches about 4～7 times in each direction, be more preferably to stretch about 5 times, and preferably from 130 to 150 ℃ of orientation temperatures, about 130 ℃ is most preferred.
With polypropylene/granulated glass sphere composition, this mixture preferably contains about 33.5%(weight) polypropylene, the consumption of granulated glass sphere filler is in 55～65%(weight) in the scope better, be preferably 65%.The calcium stearate consumption is preferably about 0.5～2.0%, and most preferably 1.5%.The biax orientation of film is to stretch 4～7 times better in each direction, preferably 5 times, and preferably from 130 to 150 ℃ of orientation temperatures, about 135 ℃ is most preferred.
With polybutene/calcium carbonate composition, this mixture contains about 65～75%(weight) filler is better, and is more preferably about 70%, the amount of used calcium stearate should be in about 0.2～4%(weight in said composition) and in the scope, more preferably 2%.This film biax orientation should be about 1.5～5 times, is preferably 4 times, about 20～105 ℃ of temperature range, about 100 ℃ best.
With polyethylene/calcium carbonate composition, amount of filler is in about 60～70%(weight) in the scope better, more preferably about 70%.The consumption of calcium stearate about 0.1～3.5% is better in said composition, and more preferably 0.5～2%.This film biax orientation about 1.5～5 times better, more preferably about 4 times, about 20～110 ℃ more preferably 100 ℃ of temperature range
This mixture preferably contains about 0.1～2%(weight) stablizer, preventing to be exposed to ultraviolet ray, oxygen and produce degraded when being heated, this is effective especially for containing polypropylene and poly composition.
After film composite prepares, can be under the machinable temperature of matrix polymer, be made into film of the present invention with any currently known methods that is suitable for the thermoplastic polymer melting mixing, preferably use high shear mixing, this can finish in Banbury type or another kind of heavily stressed mixing tank or continuous mixing device (as forcing machine).Each component does not need pre-mixing, but carries out pre-mixing without detriment to enforcement the present invention, and can improve performance in some cases.
Each component melts of the present composition is mixed, make this mixture thing water content keep below per 1,000,000/(ppm) 700 parts threshold value, be preferably lower than 300ppm, preferable methods be on the travelling belt that moves by flowing air, cool off simultaneously and the water content of the composition of extruding that keeps mixing.Line thigh and particle that this air-cooling forms, its residuary water deal is well below the water content that the refrigerative method is reached in water-bath with common employing.
With ordinary skill with the granulation of line thigh, in order accurately to reach this water content, need carry out the sensitive moisture determination, for example, stop the moisture content value that volumetry (using Beckman 652 type KF coulomb meters) is estimated composition for the water content of measuring this component can use coulomb CALVER.
After mixing and definite moisture content,, said composition is transformed into any suitable shape for being processed into film; comprise particle or sheet; available any conventional art (comprising and extrude casting that pressing mold, flat film are extruded or blown film is extruded etc.) method is finished thin film fabrication.
After film is made desired shape, stretch with technology well-known in the art, carry out biax orientation, these technology comprise hydraulic transmission device, with the pinch roll or the tentering mechanism of friction-motion speed running.Can be sequentially or side by side carry out biaxial stretching, when using the operation of tentering mechanism, use order biaxial stretching is better.
According to the present invention, in order to reduce the moisture content in the too wet consequently out of use particle, can use another kind of method vacuum-drying, make it keep required water content (be lower than 700ppm, be preferably lower than 300ppm).In this case, with the particle that common water-bath cooling preparation is made up of polymkeric substance and filler, it contains excessive residual water content.Make these too wet particles be in partial vacuum (preferably heating) for some time, in the spendable limited range of water content in above-mentioned definition to quicken this process.Because the extra vacuum drying step of this process need, so not best method.
Also have that a kind of to keep the method for required water content be the forcing machine of directly the heat fusing thing being packed into, from mould, extrude casting spare.In this case, the fused composition is not exposed in the water, and has the low residue moisture content of above-mentioned definition, therefore can be made into smooth and foundry goods high-orientation.
Stretch ratio is at least 2 times of original size and acquires a special sense, and the film that its is produced is at least 30% hole, and the result forms the very high film of relative density.Yet, for the very low film of production relative density, being preferably on the orthogonal direction film stretching at least 3～8 times to its original size, the film that the result forms has about 40～70% holes.
Certainly, more than the glass transformation temperature of matrix polymer (preferably high at least 20 ℃) and below the melt temperature, especially stretch with interior 10 ℃ of this temperature range, the tensile temperature depends on tensile speed to a certain extent.Different polymkeric substance and composition thereof present different elasticity and visco-elasticity.Therefore, in order to obtain identical perviousness, different samples must adopt different amount of tension.Obviously, must reach tension set in order to form hole, film must stretch more than the yield-point at it.
For given composition, the big more total porosity that obtains of degree of drawing is big more, by adding more filler and measuring equally or the stretching of smaller slightly amount, can obtain higher total porosity.
In in following implementation column, unless otherwise mentioned, all umbers, ratio and percentage number average are represented with weight.
Among the embodiment 1-8, each component (being listed among the table 1A) at room temperature mixes, and mixes with twin screw extruder, pushes out-of-line stock in 243～265 ℃ of scopes of temperature.Then, the line thigh is cooled off (except embodiment 6～8 usefulness water coolings) and granulation in air.Particle 80 ℃ of vacuum-dryings 24 hours (except embodiment 7 and 8 70 ℃ of vacuum-dryings 8 hours).Use 278～282 ℃ of melt temperatures (478～540), pass through the wide seam die head of one or six English inch with single screw extrusion machine, particle is expressed to (except example 6～8 keeps 18～24 ℃) on the casting roller that remains on 65 ℃, so that form the foundry goods of 15 mil thick.Use the TMlong drawing machine, to take from the square coupons that foundry goods is of a size of 2 * 2 English inch and carry out biax orientation, on operating direction, stretch 4 times at 100 ℃, and 4 times of cross directional stretchs (except in example 8, stretch 2x * 2x doubly), the product that makes is listed in following 1.
Embodiment 9-14 each component is listed in table 1B.In embodiment 9 and 10, each component mixes under 200 ℃ in edge-runner mill simultaneously, and this mixture makes the sheet of 30 mil thick at 215 ℃ of pressing molds.From this sheet get square one of 2 English inch with the TMlong drawing machine at 140 ℃ of biax orientations, stretch 5 times at operating direction, 5 times of cross directional stretchs, the film that makes is as described in the table 1B.
In embodiment 11 and 14, each component mixes at 225-250 ℃ in twin screw extruder, the extrudate granulation and on the casting extrusion machine at 180～230 ℃ of castings.Embodiment 11, because the line thigh of much extruding in granulation stage fracture, granulation is inhomogeneous, so foundry goods can not stretch at 140 ℃ on the TMlong drawing machine, and foundry goods is too crisp.The square foundry goods of embodiment 14,2 * 2 English inch on the TMlong drawing machine at 140 ℃ of stretching 4.5x * 4.5x doubly.
Embodiment 12 and 13, each component mixes with twin screw extruder, forms the foundry goods of 30 mil thick with the extruding of single screw extrusion machine and seam die head, and this foundry goods 5x * 5x that stretches on the TM.Long drawing machine doubly makes film.
Figure 891073159_IMG2
Table 1B
9 comparative examples 10 11 12 13 14
Polymer P P/C 2C * 3PP/C 2C 3Pp pp/C 2C 3PP/C 2C 3Pp
（1∶1） （1∶1） （1∶1） （1∶1）
（%） 39.83 49.74 39.64 34.61 34.91 36.05
Calcium stearate (%) 0.32 0.40 0.40 1.04 0.17 1.09
CaCO 3（%） 59.75 49.74 59.46 64.27 64.83 -
Stablizer (%) 0.10 0.12 0.50 0.09 0.09 0.16
Granulated glass sphere (%) 62.71
Product property
*C 2C 3Be to contain the 2.7%(mole) ethylene-propylene copolymer of ethylene unit
All products that obtain among the embodiment all are the opaque and white films.
Embodiment 1a, b and c represent LLDPE/CaCO 3Film contains 70%(weight) the resulting Gurley of filler counts ratio and contains 65%(weight) the Gurley number much lower (being the ventilation property height) of filler gained.Embodiment 1a, b and c represent that the highest film ventilation property of orientation degree is best.Equally, 65%(weight) filler (embodiment 2) is more much lower than the Gurley number of 60% filler (embodiment 3) gained.The processing characteristics that embodiment 4 is added 1.5% calcium stearate (embodiment 1) with embodiment 1 comparative descriptions rather than add 0.6% calcium stearate (example 4) composition improves, and, in comparative example 4, long-pending thing bathed by mould and the fusion fracture is too much, and the molten thread stock-traders' know-how normal off that causes extruding splits.Therefore this material can not granulation and is squeezed into the foundry goods that is suitable for being orientated.Embodiment 5 explanations are added a small amount of polyacrylic advantage in LLDPE be that loft (die lines) is reduced, with such as embodiment 1a, usually can observed fusion fracture scope compare in the composition of b and c, the scope more rare than all the other foundry goods fusion fractures (die lines) significantly reduces.
Embodiment 6 shows polybutene/CaCO 3Film, 70%(weight) filler is than 50%(weight) the Gurley number much lower (being the ventilation property height) of filler (embodiment 7) gained.Example 8 relatively represents to add 1.5% calcium stearate than not adding the easier porous membrane that is processed into of stearic acid calcium (example 8) with example 6.The film that comparative example 8 makes has many observable apertures and extremely rough, can not be 100 ℃ of orientations of carrying out 4 * 4 times.Example 9 expression polypropylene/CaCO 3Film, 60%(weight) filler is than 50%(weight) the Gurley number of filler (example 10) gained is much lower.Example 11 is used the good processability of the mixture of polypropylene and ethylene-propylene copolymer than virgin pp (example 11) with example 9 comparative descriptions, because the foundry goods of example 11 can not be drawn into film at 140 ℃.The low embodiment 13 of embodiment 12 explanation and calcium stearate content relatively, calcium stearate content height has improved processing characteristics greatly, the film that example 13 obtains have big can observable aperture and very coarse.The breathable composition that embodiment 14 explanations are made up of polypropylene and granulated glass sphere filler.

Claims (25)

1, a kind of method for preparing flexible microporous membrane, this film tensile strength height, the infiltration that air and water vapor is had good penetration or " ventilation property " and liquid towards water has high hydrostatic pressure resistance, and this method comprises the steps; With alpha-olefinic polymer or multipolymer, granulated filler and as the mixture melting mixing of the calcium stearate of processing aid, make film, and this film of biaxial stretching, it is characterized in that this mixture comprises 60～75% (weight) particle diameter (referring to its diameter) and is the mineral filler or the granulated glass sphere of 10-15 micron, before making film, water content keeps below 700/1000000ths parts in the blended composition, and under about 20～160 ℃ of temperature range from both direction this film that stretches, each direction stretches about 1.5～7 times.
2, the method for preparing microporous membrane according to claim 1 is further characterized in that packing material size (referring to its diameter) is from 10 to 25 microns.
3, the method for preparing microporous membrane according to claim 1 or 2 is further characterized in that filler is a lime carbonate, and particle diameter (referring to its diameter) is about 12.5 microns.
4, prepare the method for microporous membrane according to claim 1,2 or 3, be further characterized in that before making film, the water content of blended composition remains below 300/1000000ths parts.
5, the method for preparing microporous membrane according to above-mentioned arbitrary claim is further characterized in that on the conveying belt that moves also to keep its water content simultaneously with the good mixture of extruding of flowing air cooling mixing.
6, the method for preparing microporous membrane according to above-mentioned arbitrary claim, the polymkeric substance or the multipolymer that are further characterized in that alpha-olefin are polymkeric substance or the multipolymers that contains the alpha-olefin of 1～8 carbon atom, or the multipolymer of the alpha-olefin of ethene and propylene or ethene and 4～8 carbon atoms.
7, the method for preparing microporous membrane according to claim 6, the polymkeric substance or the multipolymer that are further characterized in that alpha-olefin are polypropylene, polyethylene, polybutene, linear low density polyethylene and polyacrylic mixture, or the mixture of polypropylene and ethylene-propylene copolymer.
8, the method for preparing microporous membrane according to claim 7 is further characterized in that the polymkeric substance of alpha-olefin or multipolymer are linear low density polyethylenes.
9, the method for preparing microporous membrane according to above-mentioned arbitrary claim is further characterized in that this mixture contains about 20～37%(weight) polypropylene, filler is a lime carbonate.
10, the method for preparing microporous membrane according to claim 9 is further characterized in that this mixture comprises about 33%(weight) polypropylene, about 65%.(weight) lime carbonate, about 0.5～2%(weight) calcium stearate, foundry goods stretches 5～7 times for about 150～130 ℃ in temperature on both direction.
11, the method for preparing microporous membrane according to claim 9 is further characterized in that this mixture comprises about 2%(weight) calcium stearate, water content keeps below 300ppm, and foundry goods stretches at both direction at about 130 ℃, and each direction stretches 5 times.
12, the method for preparing microporous membrane according to above-mentioned arbitrary claim is further characterized in that this mixture comprises about 20～37%(weight) polypropylene, filler is a granulated glass sphere.
13, the method for preparing microporous membrane according to claim 12, be further characterized in that this mixture contains about 33.5%(weight) polypropylene, about 65%(weight) granulated glass sphere, about 0.5～2%(weight) calcium stearate, foundry goods stretches 5～7 times at both direction at about 130～150 ℃.
14, the method for preparing microporous membrane according to claim 13 is further characterized in that this mixture contains the 2%(weight of having an appointment) calcium stearate, water content keeps below 300ppm, and foundry goods stretches at both direction at about 130 ℃, and each direction stretches 5 times.
15, the method for preparing microporous membrane according to above-mentioned arbitrary claim is further characterized in that this mixture contains about 65～75%(weight) polybutene, filler is a lime carbonate.
16, the method for preparing microporous membrane according to claim 15, be further characterized in that this mixture contains about 28%(weight) polybutene, about 70%(weight) lime carbonate, about 0.2～4%(weight) calcium stearate, foundry goods stretches 1.5～5 times at both direction for about 20～105 ℃ in temperature.
17, the method for preparing microporous membrane according to claim 16, be further characterized in that this mixture contains about 2%(weight) calcium stearate, water content keeps below 300ppm, and foundry goods stretches at both direction for about 100 ℃ in temperature, and each direction stretches 4 times.
18, the method for preparing microporous membrane according to above-mentioned arbitrary claim is further characterized in that this mixture contains about 60～70%(weight) polypropylene, filler is a lime carbonate.
19, the method for preparing microporous membrane according to claim 18, be further characterized in that this mixture contains about 28%(weight) polyethylene, about 70%(weight) lime carbonate, about 0.1～3.5%(weight) calcium stearate, foundry goods stretches 1.5～5 times for about 20～105 ℃ in temperature on both direction.
20, the method for preparing microporous membrane according to claim 19, be further characterized in that this mixture contains 0.5～2%(weight of having an appointment) calcium stearate, water content keeps below 300ppm, and foundry goods stretches on both direction for about 100 ℃ in temperature, and each direction stretches 4 times.
21, the method for preparing microporous membrane according to above-mentioned arbitrary claim is further characterized in that this mixture contains the promising ultraviolet ray that prevents to be exposed to, and produces about 0.1～2%(weight of degraded when oxygen and heating) stablizer.
22, a kind of microporous membrane of biax orientation, it comprises the polymkeric substance or the multipolymer of alpha-olefin, granulated filler and calcium stearate, it is characterized in that it prepares with the described method of above-mentioned arbitrary claim, be further characterized in that its Gurley porosity (according to ASTM D-726 method B) is 0.1～20 second, therefore this film has good air and water vapo(u)r transmission rate, and liquid is impermeable basically.
23,, can be used as the drop cloth or the towel of slacks lining according to the application of the microporous membrane of claim 22.
24,, can be used as sheet or hospital work clothes according to the application of the microporous membrane of claim 22.
25, according to the application of the microporous membrane of claim 22, can be used as the iontophoretic injection barrier film that contains in the liquid accumulator.
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US4923650A (en) 1990-05-08
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CA1327259C (en) 1994-03-01

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